Process for breaking petroleum emulsions



Patented June 13, 1944 UNITED Search Roan STATES PATENT OFFICE PROCESS FOR BREAKING PETROLEUM EMULSIONS No Drawing. Application November 30, 1942,

Serial No. 467,476

7 Claims.

This invention relates to the treatment of petroleum emulsions, and has for its main object to provide a practical method of making the said compounds or chemical products.

Another object of our invention is to provide a novel process for resolving petroleum emulsions of the water-in-oil type, that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and Which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

Another object of our invention is to provide an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned is of significant value in removing impurities, particularly inorganic salts from pipeline oil.

Briefly described, our process consists in subiecting a petroleum emulsion of the water-in-oil type, to the action of a demulsifier comprising an oxyalkylated, drastically-oxidized, dehydrated ricinoleic acid compound.

oxyalkylation is concerned with procedure whereby compounds are subjected to reaction with a reactant having a reactive ethylene oxide ring. The most suitable oxyalkylating agents are ethylene oxide, propylene oxide, butylene oxide, glycidol, etc. However, there are other well known oxyalkylating agents. For instance, U. S. Patent No. 2,208,581, dated July 23, 1940, to Hoeffelmann enumerates the following: glycerine epichlorhydrin, glycide alcohol, ethylene oxide, propylene oxide, butene-2-oxide, butene-l-oxide, isobutylene oxide, butadiene oxide, butadiene dioxide, chloroprene oxide, isoprene oxide, decene oxide, styrene oxide, cyclohexylane oxide, cyclopentene oxide, etc.

oxyalkylation, and particularly oxyethylation, is apt to involve any labilehydrogen atom, as, for example, a hydrogen atom attached to an oxygen atom. Other reactions involving ethylene oxide or the like are those in which ester rearrangement or interchange takes place. In other instances, aldehydic or ketonic carbonyl radicals may be effective. In a general Way, oxyalkylation, and particularly oxyethylation, takes place at moderate temperatures, for instance. 150-2'00 C., under moderate pressures, for instance, not over 450 lbs. gauge pressure. Such reactions may be accelerated by means of a catalyst, such as a small amount of alkali, as, for instance, one-fourth percent of sodium methylate. 'Such reactions are conducted with constant stirring so as to promote contact with the ethylene oxide or other oxyalkylating agent. Generally speaking, the reaction or series of reactions are conducted in a step-wise manner,

i. e., if one intended to introduce 10-20 moles of ethylene oxide per mole of glyceride or its equivalent, one might introduce 2 moles of ethylene oxide at a time until approximately one-half the ethylene oxide had been introduced, and thereafter, the proportion may be increased until the total amount is introduced. The completeness of reaction is generally indicated by the disappearance of pressure, due to the presence of unreacted ethylene oxide, or the like. Since such procedure, i. e., the oxyalkylation of a glyceride is well known, further description will be avoided, for the simple reason that the oxyalkylation of blown dehydrated castor oil takes place by the same procedure, except that the conditions for oxyalkylation are somewhat more vigorous, i. e., it is more difiicult to initiate and continue the reactions. More details as to the conditions of the reaction will be found subsequently in regard to individual examples.

The expression ricinoleic acid compounds is intended to refer to ricinoleic acid, polyricinoleic acid, and particularly the glycerides of ricinoleic acid. Specifically the expression includes monoricinolein, diricinolein, ricinoleic acid, etc. Castor oil of commerce contains approximately -90% of triricinolein, and due to its availability and low cost, is the preferred raw material employed in manufacturing the compounds herein described.

It is well known that ricinoleic compounds which have not been subjected to pyrolytic dehydration, may be oxidized in various manners. This is usually accompanied by subjecting a ricinoleic compound to treatment, such as, blowing With a suitable gaseous oxidizing medium, e. g., air, oxygen, ozone, or ozonized air. Such oxidation is commonly carried out at ordinary or superatmospheric pressure (up to about 200 lbs. per square inch) either moist or dry; and in the presence or absence of a catalyst, such as lead oleate, cobalt linoleate, or manganese oleate, or such as, alpha-pinene or linseed oil, etc. Care should be taken, however, not to permit temperature rise such that excessive pyrolytic decomposition would take place. The oxidation may be vigorous as by vigorous blowing, or may be more gradual as by exposure in thin films to air, provided the oxidation is sufiiciently prolonged to obtain the desired drastic oxidation. Usually, the time required is at least about 8 to 10 hours, under conditions most favorable to oxidation, e. g., blowing at a relatively high temperature, and for certain fatty compounds much more prolonged oxidation, e. g., several days, or even weeks, is desirable, especially under conditions less favorable to rapid oxidation. In any event, whether the oxidation is produced by continued mild oxidation, or by more vigorous oxidation, a condition of drastic oxidation is indicated by changes in chemical and physical attributes of the material. These changes are usually indicated by a lowered iodine value, an increased Saponification value, usually an increased acetyl value, an increased specific gravity, and an increased refractive index. Thus, the iodine number may become less than 70, and even as low as about 40. The saponification value may be about 215 to about 283, and the acetyl value may be about 160 to about 200. The viscosity is increased and the drastically-oxidized product may become very heavy and stiff at ordinary temperatures. The refractive index is also increased. The color of the drastically-oxidized material may be a pale yellow or light amber, or may be a deep orange color. If oxidation is carried on long enough, a product of liver-like consistency and dark color is obtained, but since such material is more diificult to utilize, those drastically-oxidized ricinoleic compounds which are pale blown and have some fluidity at normal temperatures are preferred.

The same sort of procedure which is used to oxidize ricinoleic acid compounds which have not been subjected to pyrolytic dehydration, such as ordinary castor oil of commerce, may also be employed to oxidize dehydrated castor oil, or similar material of the kind herein intended as a primary raw material. Generally speaking, however, the following modifications should be kept in mind:

Such materials are apt to contain at least a significant amount of octadecadiene 9,11-acid-1 or its ester, which is recognized as a powerful catalyst for promoting oxidation of castor oil or similar materials. Thus, it is rarely necessary to add any catalyst to hasten oxidation. Furthermore, it is rarely necessary to oxidize under pressure, although such procedure may be employed. It is rarely necessary to use oxygen instead of air. It is rarely necessary to oxidize at a temperature above 120 C. Thus, notwithstanding the fact that any of the usual procedures employed for oxidizing castor oil may be employed for oxidizing dehydrated castor oil, yet generally speaking, considerably less drastic conditions are required. Furthermore, the time element can be decreased greatly. The same sort of apparatus and the same sort of procedure is employed as in the case of conventional oxidation of castor oil. Since dehydrated castor oil is already polymerized to a greater or lesser degree, and perhaps has initial viscosity considerably greater than that of castor oil, it is obvious that the final stages of oxidation must be carried out more cautiously, and that excessive oxidation may produce a solid or spongy or rubber-like material without previous indication of the imminent critical stage. In any event, the material prior to oxidation should be analyzed and oxidation should be conducted until there is a significant change, as indicated by increase in viscosity, change in such indices as iodine number, hydroxyl number, etc., all of which is obvious to those skilled in the art. As a matter of fact, unless one desires to do so, there is no need to oxidize such dehydrated castor oil, insofar that various products of this kind are sold commercially and used in other arts which have no particular connection with the usage herein contemplated.

Castor oil, or similar materials of the kind described, have been dehydrated, and such dehydrated materials used for various other purposes, for instance, as substitutes for drying oils, as plasticizers in the manufacture of resins, as

ingredients entering into the compounding of insulating materials, etc. Generally speaking, the conventional procedure is to subject a quantity of castor oil to destructive distillation, approximately 250-310 C., and generally 250-285 C. until at least 5-15% of the original volume has been removed as a distillate. Sometimes the procedure is conducted primarily to recover the distillate, due to its high content of heptaldehyde. Generally speaking, the lower limits of the material distilled ofi are approximately 8-10%, and the upper limits, possibly 15-23%. In some instances, pyrolysis is conducted in presence of an added catalyst, which may permit the reaction, i. e., the degradation or destructive distillation, to take place at lower temperature; and sometimes vacuum is employed, or both vacuum and a catalyst. Such procedure of subjecting a ricinoleic acid body, and especially ricinoleic acid or castor oil, to a pyrolysis, is so well known that no further elaboration is required. However, for convenience, reference is made to the following patents, which clearly describe the procedure, and in some instances, point out at least some of the complicated chemical changes that take place:

U. S. Patent No, 1,240,565, Harris, Sept. 18, 1917; 1,749,463, Bertsch, March 4, 1930; 1,799,420, Holton, April 7, 1931; 1,886,538, Fanto, Nov. 3, 1932; 1,892,258, Ufer, Dec. 27, 1932; 2,156,737, Priester, May 2, 1939; 2,195,225, Priester, March 26, 1940.

British Patent No. 306,452, Scheiber, May 9, 1930.

As to a comparative evaluation of various dehydration catalysts for castor oil, see Masloboino- Zhirovanya Prom. 16, No. 5/6, 33-8 (1940).

The products which we prefer to use for reaction with ethylene oxide are blown dehydrated castor oils having substantially the following identifying characteristics within the ranges indicated:

Acid number 14.0 to 25.0

Saponification number 195 to 240 Iodine number 7 0 to Hydroxyl number 63.0 to 80.0 Reichert-Meissel number Less than 5 Acetyl number 60 to '75 Per cent unsaponifiable matter Generally less than 3 Per cent nitrogen 0.0 Per cent S02 0.0 Per cent ash Trace Specific gravity at 31 C About 0.9574 Refractive index at 31 C About 1.4795 Color Straw or light amber A specific example of a very desirable oxidized dehydrated castor oil for use in the practice of this invention and which is available in the open market, has approximately the following specific characteristics:

Acid number 18.1

Saponification number 216.5 Iodine number 83 Acetyl number 68 Hydroxyl number 71.4 Reichert-Meissel number 2.0

Per cent unsaponifiable matter Less than 2.5

Per cent nitrogen 0.0 Per cent S02 0.0 Per cent ash Trace Specific gravity at 31 C 0.9574 Refractive index at 31 C 1.4795

ZDZ: bUWH'UGl i lunmu The above values or similar values are of assistance in indicating and characterizing a material of the kind herein contemplated. For instance, although the entire chemistry of the dehydration of castor oil is not known, yet obviously there must be a marked reduction in the acetyl or hydro'xyl value, and simultaneously an increase in the iodine value. Also, such pyrolytic reaction tends to eliminate the low molal or volatile acids. On oxidation of such material, the acetyl value or hydroxy1 value may stay constant or increase. But, in any event, the iodine value is reduced until it begins to approximate that of castor oil or ricinoleic acid prior to dehydration, or somewhat lower. The fact that the acetyl value or hydroxyl value does not increase proportionally with the drop in the iodine value is, of course, due to either the formation of ether type compounds, or oxides which do not give a hydroxyl or acetyl value, or else, due to the formation of ester acids or similar reactions. It is generally desirable that the iodine number of the drastically-oxidized dehydrated castor oil be not less than 70. that the saponification value be within the range 195 to 200 and that the acetyl value be within the range of 60 to 75.

Having obtained drastically-oxidized dehydrated castor oil or other drastically-oxidized dehydrated ricinoleic acid compounds, the next step is oxyalkylation in the same manner as previously described. Our preferred oxyalkylating agent isone having not over four carbon atoms per mole, i. e., we prefer to'use ethylene oxide, propylene oxide, butylene oxide, or glycidol. Due to its availability and low cost, together with its extreme reactivity and low molecular weight, We prefer to use ethylene oxide. For convenience, the following examples refer to ethylene oxide as the oxyalkylating agent, but obviously, other reactants may be employed:

Example 1 180 lbs. of a drastically-oxidized dehydrated castor oil of the kind described by the last tabular specification. immediately preceding, is mixed with 1 lb. of sodium stearate and then subjected to reaction in a suitable autoclave with 46 lbs. of ethylene oxide. The temperature employed is approximately 170 C., and the time approximately hours. During this'period the-gauge pressure drop was from a maximum of 320 lbs. to 0. The product so obtained has somewhat marked hydrophile properties, that is, shows a tendency towards self-emulsification.

' Example 2 The same procedure is followed as in the preceding example, except that after the initial dropto zero, a second batch, to wit, 46 lbs. more of ethylene oxide, were added, and reaction conducted for 10 hours, until therewas a drop from 300 lbs. gauge pressure to zero. The product so obtained is a self-emulsifying oil and represents a molar ratio of 1 to 12.

Example 3 136 lbs. of material obtained in the manner described in Example 2, preceding. is treated with 46 lbs. of ethylene oxide at a temperature of 170 C. for 8'hours. During this reaction period the temperature reached 'a maximum of 420 lbs. and dropped to zero. This represents a ratio of 1 to 24. The product so obtained shows solubility in water, with some persistent cloudiness, al-

though markedly more soluble than the preceding example.

Example 4 A batch of material, as described in the preceding example, was prepared and treated with an- "additional 136 lbs. of ethylene oxide. Substantially the same temperature, time and pres sure conditions were employed as in the preced-- ing example. This product represented a molar ratio of 1 to 48. It was readily soluble in water to give a clear solution Without any disturbance or turbidity. The product is distinctly more water soluble than the preceding example.

Attention is directed to a fact which has already been emphasized to a greater or lesser degree, and that is, that the chemistry involved in the dehydration of castor oil or a similar ricinoleic acid compound, cannot be clearly and completely described. This is also true in regard to the second step, i. e., the drastic oxidation ofsuch dehydrated castor oil or equivalent compound. There is no adequate description of the chemical changes which take place during such oxidation procedure. Finally, since there is no suitable way of describing drastically-oxidized dehydrated castor oil, except in terms of its method of manufacture, it is equally obvious that the same procedure must be relied upon to describe oxyalkylated derivatives. Furthermore, it must be remembered that the type of reactions which take place are more complicated than those involved when one oxyalkylates a simple glyceride, such as triolein.

Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water; petroleum hydrocarbons, such as gasoline,'kerosene,'stove oil, a coal tar product,

such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents, such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials herein described, that are used as the demulsifier in our process may be admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials may be used alone, or in admixture with other suitable well known classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oil and water solubility. Sometimes they may be used in a form which exhibits relatively limited oil solubility. However, since such reagents are sometimes used in a ratio of 1 to 10,000, or 1 to 20,000. or even 1 to 30,000, such an apparent insolubility in oil and water is not significant, because said reagents undoubtedly have solubility within the concentration employed. This same fact is true in regard to the material or materials herein described.

We desire to point out that the superiority of the reagent or demulsifyingagent contemplated in our herein described process for breaking petroleum emulsions, is based upon its ability to treat certain emulsions more advantageously and at a somewhat lower cost than is possible with .rch Room other available demulsifiers, or conventional mixtures thereof. It is believed that the particular demulsifying agent or treating agent herein described will find comparatively limited application, so far as the majority of oil field emulsions are concerned; but we have found that such a demulsifying agent has commercial value, as it will economically break or resolve oil field emulsions in a number of cases which cannot be treated as easily or at so low a cost with the demulsifying agents heretofore available.

In practising our improved process for resolving petroleum emulsion of the water-in-oil type, a treating agent or demulsifying agent of the kind above described, is brought into contact with or caused to act upon the emulsion to be treated, in any of the various ways, or by any of the various apparatus now generally used to resolve or break petroleum emulsions with a chemical reagent, the above procedure being used either alone, or in combination with other demulsifying procedure, such as the electrical dehydration process.

The demulsifier herein contemplated may be employed in connection with what is commonly known as down-the hole procedure, i. e., bringing the demulsifier in contact with the fluids of the well at the bottom of the well, or at some point prior to their emergence. This particular type of application is decidedly feasible when the demulsifier is used in connection with acidification of calcareous oil-bearing strata, especially if suspended in or dissolved in the acid employed for acidification.

We have found that the most valuable products by far are obtained by use of the oxyalkylating agent, for instance, ethylene oxide, within the ratio of 12 to 30 moles of ethylene oxide per mole of original glyceride, i. e., castor oil, or 4 to moles of ethylene oxide per mole of ricinoleic acid originally employed as the raw material.

Attention is directed to the fact that in Examples 2, 3 and 4, preceding, the molecular weight of the drastically-oxidized dehydrated ricinoleic acid compound was taken arbitrarily to be 1000, in figuring the molar ratios of oil to ethylene oxide of 1-12, 1-24 and 1-48, respectively.

The new materials or compounds herein described form the subject matter of our divisional application Serial No. 491,734, filed June 21, 1943.

Having thus described our invention, what we claim and desire to secure by Letters Patent is:

1. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier comprising an oxyalkylated drastically-oxidized dehydrated ricinoleic said compound.

2. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier comprising an oxyalkylated drastically-oxidized dehydrated ricinoleic acid compound, in which the radicals introduced by oxyalkylation were selected from the class consisting of ethylene oxide radicals, butylene oxide radicals, propylene oxide radicals, and glycidol radicals.

3. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier comprising an oxyethylated drastically-oxidized ricinoleic acid compound.

4. A process for breakin petroleum emulsions of the water-in-oil type, characterized by sub jecting the emulsion to the action of a demulsifier comprising an oxyethylated drastically-oxidized castor oil obtained by oxidation of dehydrated castor oil derived by a pyrolytic step, in which the distillate was equal to at least 8% and not more than 23% by volume of the original castor oil.

5. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier comprising an oxyethylated drastically-oxidized dehydrated ricinoleic acid compound obtained by oxidation of dehydrated castor oil derived by a pyrolytic step, in which the distillate was equal to at least about 8% and not more than about 23% by volume of the original castor oil; with the added proviso that the iodine number of said oxidized product is not less than 70, the saponification value within the range of about 195 and about 240, and acetyl value within the range of about 60 to about 75.

6. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier comprising an oxyethylated drastically-oxidized dehydrated ricinoleic acid compound obtained by oxidation of dehydrated castor oil derived by a pyrolytic step, in which the distillate was equal to at least about 8% and not more than about 23% by volume of the original castor oil; with the added proviso that the oxidized dehydrated castor oil has approximately the following characteristics:

Acid number 18.1 Saponification number 216.5 Iodin number 83 Acetyl number 68 Hydroxyl number 71.4 Reichert-Meissel number 2.0

Per cent unsaponifiable Less than 2.5

Per cent nitrogen 0.0 Per cent S02 0.0 Per cent ash Trace Specific gravity at 31 C 0.9574 Refractive index at 31 C 1.4795

7. A process for breaking petroleum emulsions of th water-in-oil type, characterized by sub- Jecting the emulsion to the action of a demulsifier comprising an oxyethylated drastically-oxidized dehydrated ricinoleic acid compound obtained by oxidation of dehydrated castor oil derived by a pyrolytic step, in which the distillate was equal to at least about 8% and not more than about 23% by volume of the original castor oil; with the added proviso that the oxidized dehydrated castor oil has substantially the following characteristics:

Acid number 14 to 25 Sapom'fication number 195 to 240 Iodine number 70 to 95 Hydroxyl number 63 to Reichert-Meissel number Less than 5 Acetyl number 60 to '75 Specific gravity at 31 C About 0.9575 Refractive index at 31 C About 1.4795

and substantial freedom from unsaponifiable material, nitrogen, S02, and ash.

MELVIN DE GROOTE. BERNHARD KEISER. 

